Fluorescent polycarbonamides

ABSTRACT

Nylons are conventionally prepared by the condensation polymerization of diamines with dibasic acids. If there is incorporated into the polymerization charge from about 0.1 to 100 moles per 10,000 moles of conventional dibasic acid; a diacid, diester, diamide diacid chloride or diamidediamine of a fusedring, polynuclear aromatic hydrocarbon having at least three fused rings, the thereby resulting nylon is fluorescent.

ilnited States Patent Goetz 51 June 6,1972

[54] FLUORESCENT POLYCARBONAMIDES [72] Inventor: Frederick J. Goetz,Cedar Knolls, NJ.

[73] Assignee: Allied Chemical Corporation, New York,

[22] Filed: Aug. 24, 1970 121 App]. No: 66,603

[52] US. Cl ..260/78 R, 260/312 R [51 Int. Cl ..C08g 20/20 [58] FieldofSearch ..260/78R [56] References Cited UNlTED STATES PATENTS 3,301,8271/1967 Martin ..260/78R 3,542,734 11/1970 Rippie ..260/78R PrimaryExaminer-Harold D. Anderson Attamey-Arthur J. Plantamura and Herbert G.Burkard [57] ABSTRACT 4 Claims, No Drawings 3 ,668, 1 89 l 2 FLUORESCENTPOLYCARBONAMIDES Amide or phenyl or alkyl ester derivatives of thedibasic acid moiety can also be utilized. In such cases, the amineBACKGROUND OF THE INVENTION moiety of the diamine replaces the amine,phenol or alcohol This invention relates to fluorescent nylons. Linearpolya- P P f P ig amide ester which amine, P1161010! mides are generallyformed by either the self-condensation 5 alcohol Fhmmated 9 Ipolymerization of amino acids or by the condensation of solmonpolymenzPuonv a f and a dlecld ride diamines with dib i a id or withamide f i g deriva are reacted together dissolved in inert organicsolvent in tive of such dia id Lin polyamides b both types are thepresence of an organic base acid acceptor such as a tertiagenerallyreferred to as nylons. This invention is concerned ry amme- For example:

0 O IINH2(CH:)5NH2 nCliiXCmpi JCl r Et N (excess) with nylons preparedby the condensation of diamines with Emulsion, i.e. interfacial,polymerization is generally cardibasic acids or with amide formingderivatives of said dibasic 2o ried out at low temperature and involvesadding the diacid acids. Such nylons can be represented by thestructural formuchloride in a water-immiscible solvent to an aqueoussolution la: of diamine, inorganic base and a surfactant. Polymerizationtakes place in the organic layer at the phase interface. The inorganicbase reacts with the HCl evolved in the reaction in I I R analogousfashion to the tertiary amine in the fully nonaque- HzNRNHTR(.LNHRNH-iJRiiOH OuS system.

wwwhmwl My invention relates to modified nylon and to a process forproducing it. More particularly, my invention relates to fluorescentnylon. The phenomenon of fluorescence connotes the production of visiblelight by a substance as the result of exposure to and absorption ofelectromagnetic radiation of a different wavelength. As used in theinstant application, the term fluorescence is restricted to the emissionof visible light on exposure to ultraviolet or near-ultraviolet visiblelight.

Since daylight and virtually all artificial light contains substantialultraviolet radiation, a fabric having the property of fluorescence willshimmer or glow on exposure to such daylight or artificial light. Suchan effect is extremely striking in clothes or upholstery or in otherdecorator applications.

The prior art contains much teaching of ways to produce fluorescentfabrics. As is obvious, a fabric would be fluorescent when the fiberfrom which it is woven is fluorescent. The prior art has preparedfluorescent fabrics by 4 physically incorporating fluorescent compoundsinto a fiber fonning polymer and then preparing fiber and ultimatelyfabric from the polymer-fluorescent compound blend. This is analogous tothe production of colored fabric by the incorporation of pigments intopolymers which polymers are then formed into fibers and the fibers intofabric. This method of wherein R and R" represent that portion of thediamine or diacid molecule, respectively, to which the two amine or twocarboxylic acid moieties are appended. While such portions, i.e.bridging groups, of the molecule can be a linear or branched chainaliphatic, alicyclic or aromatic hydrocarbon or may even contain heteroatoms, as a practical matter the commercially useful nylons utilizeeither a linear aliphatic or alicyclic hydrocarbon or a benzene ring asbridging groups. The commonly used descriptive nomenclature for suchnylons utilizes two numbers. The first number connotes the number ofcarbon atoms separating the nitrogen atoms of the diamine, the secondconnotes the number of straight-chain carbon atoms in the dibasic acid.For example, nylon 6,6 is derived from hexamethylene diamine and adipicacid. The only widely used nylons not prepared from linear aliphaticdibasic acids are the so-called aromatic nylons which use isoorterephthalic acid and thus have a benzene ring as a bridging group. Insuch cases, the letter I or T is conventionally used in place ofthesecond number.

Such dibasic acids are hereinafter referred to as conven- 5O tionaldibasic acids. Examples of such conventional dibasic acids includeterephthalic, the various naphthalene dicarboxach'evmg fluorescefce hasnumerous shof'tcommgs T ylic acids, p p'biphenyl dicarboxylic acid,oxalic, malonic, sucfluorescence'lmpamng cPmpounds are mvailably fcinic, glutaric, adipic, pimelic, suberic, azelaic sebacic, and largemust be lflcorporated Such mcorporanon nonane and decane dicarboxylicacid frequently difficult to achieve, and also, the fluorescent com-Suitable diamines include the C to C polymethylene Pounds are frequentlyi out or Partly decomposed diamines, i.e. ethylene diamine tododeoamethylene diamine, mg Subsequent of polymer/fluorscem C2 to C24alicyclic diamines, and and p phenylene diamine pound blend.Additionally, such pigments can adversely affect The term alicyclicdiamines as used herein encompasses the thermal and/01' oxldatweStablllty of the P y both mono and polycyclic compounds such ashydrogenated which they are incorporated methylene dianiline,hydrogenated isopropylene dianiline and SUMMARY OF THE INVENTION p,p'bis2(p-aminophenyl)propyl]benzcne.

In preparing such polyamides, either m t, emulsion, in- It is an objectof this invention to provide a modified nylon terfacial, or solutionpolymerization techniques may be utilpolymer which polymer, itself,inherently possesses the proized. 5 perty of fluorescence.

melt p ym molten diamine and r xyli As heretofore indicated, nylons areconventionally formed acid are reacted together, accompanied by theelimination of by the reaction of a diamine with a dicarboxylic acid oran water. For example, in preparing nylon 6,6: amide fon-n'ing reactivederivative of such acid.

It has now been found in accordance with the instant invention that if avery small percentage of the conventional diacid or derivative thereofwhich is utilized in the nylon forming polymerization mixture isreplaced by the diacid, or amide forming derivative thereof of a fusedring, polynuclear aromatic hydrocarbon having at least three fusedrings, the thereby resulting nylon is inherently fluorescent.

Specifically, l have found that if from 0.1 to 100 moles of a fused ringpolynuclear aromatic hydrocarbon diacid having at least three fusedrings are substituted for conventional diacid per 10,000 moles of saidconventional diacid, the nylon produced from said acid mixture isfluorescent.

As hereinafter used, the term diacid or dibasic acid connotes either adicarboxylic acid or a diacid chloride, diester or diarnide derivativethereof which will react with diamines to form a polyamide since eitherdiacids or derivatives thereof which will react with diamines to formpolyamides can be utilized to prepare the polyamides of the instantinvention.

Diacids of the following fused ring polynuclear aromatic compounds aresuitable: anthracene, benzanthracene, benzopyrene, benzoperylene,chrysene, coronene, dibenzanthracene, perylene, benzo[c]phenanthrene,picene, pyrene and tetracene. The location of the carboxyl moieties onthe fused rings is not critical, i.e. they can be adjacent ornonadjacent on the same ring or on different rings.

Suitable diacids include for example anthracene 1,5 and 1,8 dicarboxylicacid, perylene 3,9 and 3,10 dicarboxylic acid and 1:2, 3:4dibenzanthracene-9, 1 O-dicarboxylic acid.

The polynuclear aromatic diacids of the instant invention can berepresented by the generic formula:

wherein R connotes a fused ring polynuclear aromatic moiety having atleast three fused rings, and R connotes Cl, CR or Nl-lR wherein R ishydrogen or an alkyl, alicyclic or aromatic hydrocarbon of up to 12carbons. If R contains more than 12 carbons it is insufficientlyvolatile to be removed in the course of the polyamide formation andhence the polyamide formation reaction will generally not go tocompletion.

We have found that the polynuclear aromatic diacids utilized to preparethe fluorescent nylons of the instant inventio' n react in such afashion that both carboxyl moieties thereof react with diamine to affordsome of the amide units of the polyamide chain.

Such polyamide unit formation can be schematically represented asfollows using hexamethylene diamine as the diamine:

In the course of reaction R l-l is ordinarily removed continuously todrive the polymerization to completion.

in the polyamides of the instant invention, each polyamide chain willordinarily on the average have present amide units formed from thepolynuclear fused ring aromatic diacid as shown in (l) and also unitsfrom the convention diacid such as adipic, phthalic and the like ashereinabove enumerated. The ratio of amide units formed from saidpolynuclear aromatic diacid to conventional diacid derived amide unitsin any given polyamide chain will ordinarily be dependent upon the moleratio of polynuclear aromatic diacid to conventional diacid in thepolymerization charge. As heretofore indicated, the mole ratio ofpolynuclear aromatic diacid to conventional dibasic acid can suitablyvary from about 0.1 to about 100 moles per 10,000 moles. The ratio ofpolynuclear aromatic diacid to conventional dibasic acid derived amideunits in any given polyamide chain can of course be higher or lower thanthe exact ratio of diacids in the polymerization charge. If the ratio ofpolynuclear aromatic diacid to conventional dibasic acid isexceptionally low, it is possible that some polyamide chains willcontain no polynuclear aromatic diacid derived amide units. However, onthe average, each polyamide chain will contain the same ratio ofpolynuclear aromatic diacid to conventional dibasic acid derivedpolyamide units as is present in the polymerization charge.

As an alternative to reacting polynuclear aromatic diacid directly withdiamine simultaneously with reacting conventional diacid with diamine,the polynuclear aromatic diacid can be incorporated into the polyamidechain in a two-step process. That is, each mole of polynuclear aromaticdiacid can be reacted with two moles of the diamine of choice to form amolecule of the following structure (using hexamethylene diamine as anexample):

This diamide-diamine will than react further, along with unreacteddiamine, with conventional diacid to form the desired polyamidecontaining polynuclear aromatic diacid moieties. This procedure isactually preferred since the diamidediamine has essentially the samereactivity as the diamine from which it is prepared thereby helping toensure substantially homogeneous distribution of the polynucleararomatic diacid moieties throughout the polyamide polymer chains.

The manner in which the polynuclear aromatic diacid is incorporated intothe polyamide polymer chains is not critical, i.e., either by directreaction of polynuclear aromatic diacid plus conventional diacid withdiamine or by reaction of conventional diacid with diamine andpolynuclear aromatic diacid derived diamide-diamine as hereinbeforedescribed. The only requirement is that from 0.1 to polynuclear aromaticdiacid derived units be present in the polyamide polymer chains per10,000 conventional diacid derived units.

It should also be noted that any desired mixture of diamines or ofconventional dibasic acid or of polynuclear aromatic dibasic acid can beutilized. The only critical factor is ensuring that there be present theabove indicated ratio of polynuclear aromatic dibasic acid derived unitsto conventional dibasic acid derived units in the polyamide chains.

The fluorescent nylons of the instant invention can be prepared by anyof the conventional hereinbefore enumerated nylon synthesis methods,i.e., emulsion, solution or melt polymerization. As in conventionalnylons, ordinarily, approximately stoichiometric amounts of diamine arereacted with diacid.

Emulsion, solution, or melt polymerization techniques are suitableregardless of whether the polynuclear aromatic diacid is reacteddirectly with diamine along with conventional diacid or is firsttransformed into the diamide-diamine which is then reacted with diamineplus conventional diacid. in this latter case, the moles of conventionaldiacid present should preferably be essentially equivalent to the numberof moles of diamine plus diamide-diamine.

Likewise, the particular conventional diacid or diamine which areutilized to prepare the fluorescent nylon of the instant invention isnot critical. Any dibasic acid and diamine which are used in the art toprepare a polyamide (nylon) is suitable. The fluorescent nylon, soprepared, will be essentially identical in all nonoptical properties tothe nylon prepared from the same conventional dibasic acid and diaminewithout the inclusion of polynuclear aromatic dibasic acid. Thefluorescent nylons of the instant invention are, of course, fullyprocessable by conventional nylon processing procedures.

The invention can be more fully understood by reference to the followingexamples. All parts are parts by weight unless otherwise expresslynoted.

EXAMPLE 1 A solution of 3.0 ml sebacoyl chloride and 10 mg perylene-3,9-dicarbonyl chloride in 100 ml dry o-dichlorobenzene is v 6 carefullycovered with a solution of 4.4 g 1,6-hexanediamihe and mo] ratios ofpolynuclear aromatic dicarboxylic acid to in 50 ml water. The film whichformed at the interface was conventional dicarboxylic acid. In all runsthe reaction solvent pulled slowly from the mixture. This film whenworked with was chloroform, the reaction time was 3 hours at reflux (temdilute sodium carbonate and dried yielded highly green perature about63C.) and 100 g of conventional dicarboxylic fluorescent fiber on fusingand drawing. 5 acid chloride was utilized. The quantities of polynucleararomatic dicarboxylic acid chloride were ioned to provide the ap EXAMPLE2 propriate mole ratio. The amount of diamine utilized was the CrudeN,N'-bis(6amino-l-hexyl)-perylene-3,9-diearb molar equivalent of theconventional dicarboxylic acid plus i was prepared by addition f asolution f 50 mg polynuclear aromatic dicarboxylic acid present. In allcases pery1ene 39 dicarbony1 chloride in 5 ml warm, dry excesstriethylamine was used to neutrahzethe evolved HCl. dichlorobenzene to asolution of 5 g 1,6-hexane diamine in Reaction was Fficted p y yvdlssdvmg' ccfhvehfiohhl 1 0 ml dry -dichlol'obenzene. The greater part fth Solvent dicarboxylic acidchloride, polynuclear aromat c dicarboxylicwas removed in vacuo and the diamide precipitated with hexacld chlondedamme f methyl mm m am, treated with dilute sodium hydroxide a washedwith refluxing for 3 hours, cooling to room temperature, filtering warmwater. The dry diamide-diamine was employed instead Off the Precipitatedf y hydrochloride and of perylene3,9-dicarbonyl chloride following theprocedure stripping off excess methyl amme and chloroform h of Exampleintensely fluorescent fib were 'again residue was washed with water andthen extruded as a demtained. 1 er monofilament fiber. In all cases themonofilament fiber was fluorescent.

I 7 EXAMPLE 3 It should be noted that concentrations of polynuclear aro-I matic dibasic acid in excess of 1 mole percent based on the T0 20 8 ofhexahelhylehediamine'adipic acid Salt (P 0f 1 conventional diacid areperfectly operable to produce Percent aqueous Solution was in a p ly rtube Was fluorescent nylons. However, concentrations in excess of 1added 10 mg N,N'-bis(6-amino-2-hexyl)-3,9-perylenedicar mole ercent donot produce a significantly greater boxamide prepared as in Example 2.The cont nts of th tu fluorescent effect and because of thecomparatively high cost .were carefully purged with nitrogen so as toreplace ll ir of polynuclear aromatic dibasic acids, concentrations inextherein with nitrogen. The tube was then evacuated and cess of 1 molepercent result in a substantial increase in the sealed. The contentswere heated to 215 C. for 2 hours. After cost of the nylon.

Moles polynuclear aromatic diacid per I 10,000 moles con- Run DiemlneConventional diacid Polynuclear aromatic diacid ventional diacidAnthracene 1,5-dlcarboxylic 0, 1

. .do l0 Anthracene 1,8-d1carboxylic 10 Perylene 3,9-dlearboxylic. 10

Perylene 3,10-dicarboxylie 10 1:2,3z4 dibenzylanthracene-9, 10

Anthracene 1,5-dicarboxylic 10 Dodeeamethyleno diamine. .do V 1p-Phenylene diamine Terephthallc. 1

Hydrogenated methylene dlanillne .do l

Tetramethylene diamine Sebacic 1 d 1,4 naphthalene dicarboxylic 10 16 do1,4-cyelohexane dicarboxylic. 1

16., 1,4-diamlnooyclohexane 0 Y 1 cooling to room temperature, the sealwas broken and, under I claim:

.nitrogen, the temperature of the tube contents was raised to 1. A syn hfibef-fofmlhg Polycarbohamlde 260-270 C. A slow stream of nitrogen wasallowed to pass wherein 0.001 to 1 percent of the recurring carbonamideunits through the mixture and a vacuum of about 0.5 mm was mainh ve he Sc r tained above it. When maximal viscosity was reached, the melt wascooled under nitrogen. A yield of 14 g of bright green "0 O H Hfluorescent polymer was thereby obtained. On extrusion of g l thispolymer beautiful, intensely fluorescent fibers were ob- I v tained.Attempts to leach the fluorescent material by dissoluin acid andPTeCiPitatiQh with excess aqueous base wherein R is a member selectedfrom the group consisting of did hot-affect the fluofescehsepolymethylenes of 2 to 12 carbons, C to C alicyclic h drocarbons, henlene, and p,p'diphenyl methane and EXAMPLE 4 wherein R, is a used ringpolynuclear aromatic hydrocarbon A polymerization was carried using theprocedure of Exammoiety having 5 three fused pie 3 (except that 6 mg of3,9-perylenedica.rboxylic dichloride Polyamlde m accordafme clam where!"was utilized instead of the N,N, bis(6 amino l hexyl) 39 fusedrmgpolynuclear aromatic hydrocarbon 1s selected fromperylenedicarboxamidg.) The polymer resulting was similar in the groupconsisting of anthracene, perylene and 1:2, 3:4

chemical, h sical a dv t' al ro ert'es to that obtained in 6dibenzathracene' Example y 0p lc P p l 3. A polyamide in accordance withclaim 1 wherein said R 18 a C to C polymethylene. 7 EXAMPLE. 5 4. Apolyamide in accordance with claim 3 wherein said R is hexamethylene. Aseries of solution polymerizations was carried out utilizing 7O v avariety of diamines, conventional dicarboxylic acid chlorides,polynuclear aromatic dicarboxylic acid chlorides

2. A polyamide in accordance with claim 1 wherein said fused ringpolynuclear aromatic hydrocarbon is selected from the group consistingof anthracene, perylene and 1:2, 3:4 dibenzathracene.
 3. A polyamide inaccordance with claim 1 wherein said R is a C2 to C12 polymethylene. 4.A polyamide in accordance with claim 3 wherein said R is hexamethylene.